DE2642054A1 - PHOSPHORIC ACID AMIDESTERS, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS INSECTICIDES, ACARICIDES OR NEMATICIDES - Google Patents

Description

Phosphoric acid amide esters, processes for their preparation and their use as insecticides, acaricides or nematicides

The present invention relates to new phosphoric acid amide esters, a process for their preparation and their use as insecticides, acaricides and nematicides.

U.S. Patent No. 3,716,600 describes that a large Number of compounds of the general formula

RY. O SO ₉ R "

P - N (VIII)

R ¹ S ^ H

R alkyl with 1-3 carbon atoms, R ^{1 is} an aliphatic radical with 1-3 carbon atoms,

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R "is alkyl with 1-10 carbon atoms, cycloalkyl with 3-8 carbon atoms or phenyl and

Y signify oxygen or sulfur, have insecticidal and acaricidal activity.

So far, parathion has been used in the broad field of insecticides, especially to combat the Rice stem borer, and plant and leaf hoppers, all of which are insects that damage rice plants. The use however, parathion has been banned in many areas of the world. In particular in Japan, because although there is possesses excellent effectiveness against the pests, there is a possibility that a hazard due to acute Toxicity to mammals exists.

In addition, larger amounts of organophosphorus compounds such as parathion ^ EPN, BAYCID and Sumithioh, organochlof compounds - such as BHC, DDT, and carbamate compounds like Se> vin, always that more frequently observed phenomenon on that the pests against these chemicals become resistant.

There is therefore a need for new pesticides which have only low toxicity towards warm-blooded animals have ^ but against those pests that have achieved resistance to known chemicals are effective.

The present invention relates to phosphoric acid amide esters the general formula

R ¹ OXR ²

/ P -IT. CH-CH ₂ CH ₂ S SO ₂ R ⁵ (i)

R ^{1 stands} for methyl or ethyl

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R ^{2 stands} for C -C alkyl, alkenyl, aralkyl or a group of the general formula

worm

AC- Cκ - alkyl or halogen and m is O, 1, 2 or 3, R for C -C, -alkyl, which is optionally carried out by

Halogen is substituted,

or a group of the general formula

fc

wherein

B halogen, C -C / - alkyl, nitro or C ..- C ^ -alkoxy, and

k is 0, 1, 2 or 3 and X is oxygen or sulfur.

It was found that the compounds

of the formula I exceptionally strong insecticidal, acaricidal and have nematicidal activity and, moreover, higher activity and broader control effect as compounds of the general formula (Viii). they show especially excellent activity against spider mites, which against various organophosphorus pesticides have acquired great resistance.

R in formula (i) preferably denotes C ₁ -C 4 -alkyl, an alkenyl radical, such as, for example, vinyl, allyl, propeiiyl and metallyl (particularly preferably allyl), arylalkyl, such as, for example, benzyl and 2-phenylethyl (particularly preferably benzyl ), optionally by 1 to 3 »in particular 1 or 2, substituents, especially chlorine and C -C, alkyl (especially

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special methyl), substituted phenyl, and RC ₁ -Ci halogen-C to C.-alkyl, e.g. bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-chlorobutyl, 4-chlorobutyl, l-methyl-2- chloropropyl, 1-methyl-3-chloropropyl, 1-chloromethyl ethyl, 1-chloromethyl-2-chloroethyl and, in particular, chloromethyl, optionally with 1 to 3 substituents, in particular C -C alkyl, in particular methyl, halogen, in particular chlorine and bromine, C -C alkoxy, especially methoxy, and nitro-substituted phenyl.

The present invention also relates to a process for the preparation of the compounds of general Formula (i), which is characterized in that a phosphoram oxdothioate salt of the general formula

R ¹ O

R-

.H ¹

2 3
R and R have the meaning given above and

vorm

M denotes an alkali metal atom or ammonium, with an alkylating agent of the general formula

CH ₃ CH ₂ CH ₂ .Y

(in),

_j f ~ _
wherein

Y halogen or a sulfonic acid group, or that b) a thio- or dithiophosphoryl halide of the general my formula

Nit II6

rV x

ti

-4-

'-Hal

(IV),

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R and X are as defined above and Hai is halogen with a sulfonyl amide salt the general formula

J ₂ II

2 R and R are as defined above and M is an alkali metal atom.

The phosphoramidothioate salt (II), which according to process variant a) is used can be prepared by adding a phosphoramidothioate of the general formula

(R ¹ O) ₂ P-Ii

(VI),

12 R, R and R have the meaning given above, with

a dealkylating agent of the general formula

R ^ SM ¹

(VII),

,1

M has the meaning given above and

R hydrogen, alkyl ■ or alkoxythio-

means carbonyl.

In the above formulas (III), (III) and (VIl), M is preferably sodium or potassium or ammonium, Y is chlorine, bromine, iodine, fluorine, benzenesulphonate, p-toluenesulphonate, monopropylsulphonate or sulphate; and R is hydrogen,

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C -Cj-alkyl methoxythiocarbonyl or ethoxythiocarbonyl.

The following may be mentioned as examples of phosphoramidothioate salts of the formula (II) denied by the al! -N- ^ t hansulfonyl phosphoramidothioate _f Kn lium-O-ethyl-N-methyl-Nn-butanesulfonyl-phosphoramidothioate, Kn1ium-O-methyl-N-methyl-N-benzenesulfonylphosphoramidothioate, Kn 1ium-O-Athy 1 -N-methyl -N-benzenesulfonylphosphoramidothioate, Kn 1 ium-O-ethyl-N-methyl-N-'l- chlorobenzenesulfonylphosphoramidothioate, potassium-O-ethy 1 -N-methyl-N-2, 'ί-dichlorobenzenesulfonylphosphoramidothioate, potassium- 0-Ethyl-N-methy IN-'j-methylbenzolsiiT fonylphosphoramidothiont, Kalium-O-Ethyl -N-methyl-N-'l-methoxyb-enzolsulfonyl phosphoramidothioat, Kalium-O-Ethyl-N-ine th3 ^r l -N-2-methoxy- ^t 3-chlorobenzenesulfonylphosphoramidothioate, potassium-0-ethyl-N-methyl-N-2-nil: robenzenesulfonylphosphoramidotliioate, potassium-O-ethyl-N-ethyl-N-methanesulfonyl phosphoramidothioate , Potassium-O-ethyl-N-iso-propyl-N-methanesulfonylph osphoramidothioate, Knlium-O-Ethyl-N-iso-propyl-N-chloromethanesulfonylphosphoramidothioate, Potassium-O-Ethy1-N-isο-propyl-N-benzenesulfonylphosphoramidothioate, Potassium-O-Ethyl-Nn-butylphosphor1-N-mothonylphosphorus O-ethyl-N-allyl-N-methylsulfonylphosphoramidothioate, potassium-O-ethyl-N-allyl-N-benzenesulfonylphosphoramidothioate, potassium-O-ethyl-N-phenyl-N-methanesulfonylphosphoramidothioate, ethyl-N-O- -phenyl-N-benzenesulfonylphosphoramidothioate, potassium-0-ethyl-N-Ί-oh lorphenyl-N-meth.-nsulfonylphosphoramidothioat, Kalium-O-Athy 1-N - ^ - methylphenyl-N-methanesulfonylphosphoramidothioat, Kalium-O -Ethyl-N- (2-methy1-4-chlorophenyl) N-methanesulfonylphosphoramidothioate, potassium-O-ethyl-N-benzyl-N-methanesulfonylphosphoramidothioate, potassium-O-methyl-N-methyl-N-methanesulfonylphosphoramidothioate, potassium-O- Ethyl-N-2-methylphenyl-N-mei hansulfonj ^ lphosphoramidothioat, potassium-O-ethyl-N-2, Ί-dimethylphenyl-N-methanesulfonylphosphoramidothioat, potassium-O-ethyl-N-2, Jl-dichlorophenyl-N- methansul phonylphosphoramido-

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thioate, potassium-0-ethyl-N- (2-methyl-4-chlorophenyl) -N-benzenesulfonylphosphoramidothioate, potassium-O-ethyl-N-methyl-N- chloromethanesulfonylphosphoraraidothioate, potassium-O-jithyl-N-methyl-N- 4-bromobenzenesulfonylphosphoramidothioate and potassium-O-ethyl-N-methyl-N-2,4,5-trichlorobenzenesulfonylphosphoramidothioate, and also the corresponding sodium triethylammonium, dimethylanilinium and pyridinium salts.

The following may be mentioned as examples of alkylating agents of the general formula (Hl): n-propyl chloride, N-propyl bromide, N-propylbenzenesulfonate, N-propyl-p-toluenesulfonate, Di-n-propyl sulfate and mono-n-propyl sulfate.

As examples of phosphoramidothioates the general The following formula (vi) may be mentioned: O, O-diethyl-lime ethyl-N-methanesulfonylphosphoramidothioate, 0, O-di-ethyl-N-methyl-N-ethanesulfonylphosphoramidothioate, O, O-Di-ethyl-N-methyl-N-n-butanesulfonylphosphoramidothioate, 0,0-dimethyl-N-methyl-N-benzenesulfonylphosphoramidothioate, 0, O-Di-ethyl-N-methyl-N-benzenesulfonylphosphoramidothioate, 0, O-Di-ethyl-N-methyl-N - ^ - chlorobenzene sulfonyl phosphoramidothioate , 0, O-diethyl-N-methyl-N-2,5-dichlorobenzenesulfonylphosphoramidothioate, 0, O-Di-ethyl-N-methyl-N- * f-methylbenzenesulfonylphosphoramidothioate, 0, O-diethyl-N-4-methoxybenzenesulfonylphosphoramidothioate, 0, O-Di-ethyl-N-methyl-N-2-methoxy-5-chlorobenzenesulfonyl phosphoramidothioate , 0, O-Di-ethyl-N-methyl-N-2-nitrobenzenesulfonylphosphoramidothioate , 0, O-diethyl-N-ethyl-N-methanesulfonylphosphoramidothioate , 0,0-Di-ethyl-N-iso-propyl-N-metha ^ .- sulfonylphosphoramidothioate, 0, O-diethyl-N-isopropyl-N-chloromethanesulfonylphosphoramidothioate, 0, O-di-ethyl-N-isopropyl -N-benzenesulfonylphosphoramidothioate, 0, O-di-ethyl-N-n-butyl-N-methanesulfonyphosphoramidothioate, 0,0-diethyl-N-allyl-N-methanesulfonyphosphoramidothioat, 0, O-diethyl -N-allyl -N-benzenesulfonylphosphoramido thioate, 0, O-diethyl-N-phenyl-N-methanesulfonylphosphoramidothioate,

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O, 0-Di-ethyl-N-phenyl-N-benzenesulphonylphosphoramidothioate, O, 0-di-ethyl-N-4-chlorophenyl-N-methanesulphonylphosphoramidothioate, O, O-di-ethyl-N - ^ - methylphenyl-N methanesulfonylphosphoramidothioate, 0, O-di-ethyl-N- (2-methyl- ^ -chlorophynyl) N-methanesulfonylphosphoramidothioate, 0, O-di-ethyl-N-benzyl-N-methanesulfonylphosphoramidothioate, 0, O-dimethyl -N-methyl-N-methaiisulphonylphosphoramido thioate, 0, O-di-ethyl-N-2-methylphenyl-N-methanesulphonylphosphoramidothioate, 0,0-diethyl-N-2,4-dimethylphenyl-N-methanesulphonylphosphoramidothioate, 0, O -Di-ethyl-N-2,4-dichlorophenyl-N-methanesulfonylphosphoramidothioate, 0, O-di-ethyl-N- (2-meth.yl-4-chloroph.enyl) N-benzenesulfonylphosphoramidothioate, 0, O-di- ethyl N-methyl-N-chloromethanesulfonylphosphoramidothioate, 0, O-di-ethyl-N-methyl-N-4-bromobenzenesulfonyl-phosphoramidothioate, and O, O-di-ethyl-N-methyl-N-2, k , 5-trichlorobenzenesulfonylphosphoramidothioate .

As examples of the dialkylating agents of the general formula (VIl), there may be mentioned: sodium hydrosulfide, Potassium hydrosulfide, sodium methanethiolate, potassium ethane

thiolate, sodium 2-propane thiolate, potassium methylxanthate, Potassium ethyl xanthate, and ammonium sulfide.

The method variant a) is given by the following Reaction scheme explained:

(i) (C ₂ H ₅ O) ₂ ? -

C ₂ E ₅ O

CH-

CH ₅ SO ₂ ■

• Ν

CH

+ SSH

• K + C ₂ H ₅ SH

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-8th-

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26A2054

(ii)

/ * - * Ii r— v

CH-

2 5

CH.

P - Έ

+ KB

In the above process steps, the potassium-O-ethyl-N-methyl-N-methanesulfonyphosphoramidothioate obtained in the first process step can be used to be isolated. However, it is also possible to use this salt in situ - i.e. without prior separation - with the alkylating agent to convert to the desired O-Ätlryl-S-n-propyl-N-methyl-N-methanesulfonylphosphoramidothioate in · high purity and high yield.

Process variant a) according to the present invention is preferably carried out using a solvent or diluent. Examples of such solvents or diluents are water and inert organic solvents from the group of aliphatic, alicyclic and aromatic hydrocarbons, which may optionally be chlorinated, such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, Carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene; Ether, e.g. Diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, Methylisoprop} ¹ · - ketone and methyl isobutyl ketone, nitriles, vie for example, acetonitrile, propionitrile and acrylonitrile!; Alcohols such as methanol, ethanol, iso-propanol, tert-butanol and ethylene glycol; Esters, e.g. ethyl acetate and amyl acetate; Acid amides

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and sulfoxides such as dimethyl sulfoxide and dimethyl sulfonj as well as bases such as pyridine.

Method variant a) of the present invention can be carried out within a wider temperature range. In general, the process is carried out at temperatures carried out between -2O ° C and the boiling point of the mixture, preferably at temperatures from 0 to 100C. In addition, the reaction is preferably carried out under atmospheric pressure. However, it can also with increased or reduced pressure. When proceeding according to process variant b), the halogen can be used in the general Formulas (XV) and (v), preferably chlorine, and

2
M preferably denotes potassium or sodium.

The following are examples of the thio (or dithio) phosphoryl halides of the general formula (IV) called: O-methyl-S-n-propylthiophosphoryl chloride, O-ethyl-S-n-propylthiophosphoryl chloride, O-methyl-S-n-propyldithiophosphoryl chloride, and O-ethyl-S-n-propyldithiophosphoryl chloride.

The following may be mentioned as examples of the sulfonamide salts of the general formula (v): Natriura-N-methyl methanesulf onamid, sodium N-methylethanesulfonamide, Sodium-N-methyl-n-butanesulfonamide, sodium-N-methylbenzenesulfonamide, Natriura-N-Methyl - ^ - chlorobenzenesulfonamide, Sodium-N-methyl-2,5-dichlorobenzenesulfonamide, Sodium-N-methyl-4-methylbenzenesulfonamide, Sodium N-methyl-4-methoxybenzenesulfonamide, Sodium N-methyl-2-methoxy-5-chlorobenzenesulfonamide, Sodium-N-methyl-2-nitrobenzenesulfonamide, sodium-N-ethylmethanesulfonamide, Sodium-N-iao-propylmethanesulfonamide, Sodium-N-iso-propylchloromethanesulphonamide, sodium-N-iso-propylbenzenesulphonamide, Natriura-N-n-Butylmethanesulfonamid, Sodium-N-Allylmethanesulfonamid, Sodium-N-Allylbenzolaulfonamid, Natriura-Methanaulfonanilid, Sodium-Benzolsulfonanilid, Sodium methane sulfone-4-chloranilide, sodium methane sulfone

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Jt-methylanilide, sodium methanesulphone-Z-methyl - ^ - chloranilide, sodium-N-benzylraethanesulphonamide, sodium-methanesulphone-N-2-methylanilide, sodium-methanesulphone-N-2, k dimethylanilide, sodium-methanesulphone-N-2 , ^ i-dichloroanilide, sodium methanesulfon-N-2-niethyl-ij-chloranilide, sodium trium -N-methylchloromethanesulfonamide, sodium-N-methyl-4-bromobenzenesulfonainide, and sodium-N-methyl-2, k, 5-triclilobenzenesulfonamide, and the corresponding potassium saltsc.

Process variant b) can be illustrated by the following two implementation schemes.

C ₂ E ₅ O

0 "Ρ - Cl +

Ife

C ₂ H ₅ O

Il

SO ₂ C ₂ H ₅

KkCl

C ₂ H ₅ O

"P - Cl

CH ₅ Cn ₂ CH ₂ S

SO ₂ CH ₅

+ Ha Cl

When carrying out process variant b) i ^ i preferably an inert solvent or diluent used. The solvents mentioned above in connection with process variant a) can be used

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to obtain the desired product in high yield and high purity.

Process variant b) can be used within a can be carried out over a wide temperature range. In general, the reaction is carried out at temperatures between 20.degree and the respective boiling point of the mixture, preferably carried out at temperatures from 0 to 100.degree. Although it If it is desirable to carry out the reaction at atmospheric pressure, it is also possible to carry it out at reduced pressure or to drain the increased pressure.

As already mentioned above, the phosphoric acid amide esters according to the present invention are distinguished in particular by an excellent insecticidal, acaricidal and nematicidal effectiveness. They are both against plant pests as well as harmful ones Pests (hygiene pests) and against stored pests, such as those of grain stocks, effective and combine low phytotoxicity and good effectiveness against both sucking and biting insects and against mites. Their effectiveness sets in very quickly and lasts for a long time. Because of this, the connections according to the present invention successful as pesticides for crop protection but also in the large field of hygiene and the storage protection can be used. Also on that Areas of veterinary medicine are those according to the invention Compounds against various endoparasites and ectoparasites as suitable against mites (ticks) and insects.

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The sucking insects mainly include aphids
. (Aphididae) like the green peach aphid (Myzus persicae),
the black bean (Doralis fabae), oat (Rhopalosiphum
padi), pea (Macrosiphum pisi) and potato louse (Macrosiphun solanifolii), also the currant gall (Cryptomyzu3 korscheltl), floury apple (Sappaphis mall), floury plum (Hyalopteru3 arundinis) and black cherry aphid (Myzus cerasi), also - and mealybugs (Coccina), for example the ivy shield louse (Aspidiotus hederae) and cup scale louse (Lecanium hesperidum) as well as the mealybug (Pseudococcus maritimus);
Bladder feet (Thysanoptera) such as Hercinothrips femoralia and
Bed bugs, for example the beet (Piesma quadrata), cotton (Dysdercus intermedius), bed (Cimex lectularius), predatory (Rhodnius prolixus) and Chagasvanze (Triatoma infestans),
furthermore, cicadas such as Euscelis bilobatus and Nephotettix bipunctatus.

Among the biting insects, butterfly caterpillars (Lepidoptera) such as the cabbage moth (Plutella maculi-pennis), the gypsy moth (Lymantria dispar) and golden juices should be mentioned in particular
(Euproctis chrysorrhoea) and ring moth (Malacosoma neustria), furthermore the cabbage (Mamestra brassicae) and the seed owl (Agrotis segetum), the large cabbage white butterfly (Pieris brassicae), small frost moth (Cheioatobia bruinata), oak moth (Tortrix vlridana) - (Laphygma frugiperda) and Egyptian cotton worms (Prodenia litura), also the web (Hyponomeuta padella), flour (Ephestia kühniella) and large ones
Wax moth (Galleria mellonella),

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4}

The biting insects also include beetles (Coieoptera) = ". B. Corn- (Sitophilüs granarius = Calandra granaria), Potato (Leptinotarsa decemlineata), dock (Gastrophysa viridula), horseradish leaf (Phaedon cochleariae), rapeseed (Meligethes aeneus), raspberry (Byturas tomentosus), table beans (Bruchidius = Acanthoscelides obtectus), Bacon (Derraestes Frischi), Khapra- (Trogoderma granarium), red-brown Rice flour (Tribolium castaneum), corn (Calandra or Sitophilus zeair.ais), bread (Stegobiurn paniceum), common flour (Tenebrio molitor) and grain beetle (Oryzaephilus surinamensis), but also species living in the ground, e.g. B. Wireworms (Agriotes spec.) and grubs (Melolontha melolontha); Cockroaches like the German (ELatteHa germanica), American (Periplaneta americana), Madeira (Leucophaea or Rhyparobia maderae), Oriental (Blatta orientalis), giant (31aberus giganteus) and black giant cockroach (Blaberus fuscus) and Henschoutedenia flexivltta; furthermore orthoptera e.g. the cricket (Gryllus domesticus); Termites such as the earth termites (Reticulltermes flavlpes) and Hymenoptera such as ants, for example the meadow ant (Lasius niger).

The dipteras essentially include flies such as the dew (Drosophila melanogaster), Mediterranean fruit (Ceratitis capitata), house (Musca domestlca), small house (Fannia canicularis), glossy fly (Phormia regina) and blowfly. (Calllphora erythrocephala) and the calf stick (Stomoxys calcitrans); also mosquitoes, for example mosquitoes such as the yellow fever (Aedes aegypti), house mosquito (Culex pipiens) and malaria mosquito (Anopheles Stephens!).

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The mites (Acari) particularly include the spinnaceae (Tetranychidae) like dis bean (Tetranychus telarius = Tetranychus althaeae or Tetranychus urticae) and the fruit tree spider mite (Paratetranychus pilosus = Panonychus ulni), Gall mites, e.g. 3. the common currant mite (Eriophyes ribis) and tarsonemids, for example the shoot tip mite (Kemitarsonemus latus) and cyclamen mite (Tarsonemus pallidus); sohlie31ich ticks like the leather tick (Ornithodorus neubata).

Are the invention. Anti-pest products which are particularly harmful to health, and against supplies pests used, especially against flies, and Mosquitoes are characterized by an extraordinary residual effect on wood and clay, as well as good ones Stability against alkaline or limed substrates.

The "active ingredient compounds according to the present Invention combine low toxicity against Varra-blooded animals and extremely strong nematocidal activity and can therefore be used to control nematodes, in particular phytopathogenic nematodes. There are particular called: leaf nematodes (Arphelenchoides), like the chrysanthemum elbow (A. ritzemabosi), the strawberry elbow (A. fragariae), the rice elbow (A. oryzae.); Stern inematodes (Ditylenchus), like the little stick (D. Dipsaci); Root knot nematodes (Pleloidogyne) such as M. arenaria and M. incognita; cyst-forming nematodes (Heterodera), such as the potato seedlings (H. rostochiensis), the beet burner (H. schachtii); as well as free-living root nematodes e.g. of the genera Pratylenchus, Paratylenchus, R.otylenchus, Xiphinema and Ra & opholus.

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The active ingredient compounds according to the present Invention can be in the usual formulations, such as solutions, emulsions, suspensions, powders, pastes and Granules can be transferred. These can be produced according to processes known per se, e.g. by mixing the active ingredient compound with carrier materials, such as e.g. liquids or solids, or liquefied gaseous diluents or carriers, in particular with simultaneous use of surface-active agents', such as emulsions and / or dispersants and / or foam-forming agents. In the case of using water Organic solvents can also be used as extenders, for example as auxiliary solvents.

In particular, aromatic hydrocarbons such as e.g. Xylenes, toluene, benzene or alkyl naphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic ^ Hydrocarbons such as cyclohexane or paraffins, e.g. mineral oil fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone or strongly polar solvents such as dimethylformamide, dimethyl sulfoxide or acetonitrile and water called.

Liquids which may be mentioned as liquefied gaseous diluents and / or carriers are liquids which are used in Normal temperatures and normal pressure are gaseous, such as aerosol propellants such as halogenated hydrocarbons ^ e.g. Freon.

Solid diluents and / or carriers are in particular ground, natural minerals such as kaolins, Clays, talc, lime, quartz, atapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as

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to

called highly dispersed silica, aluminum oxide or silicates. Preferred examples of emulsifiers or foam-forming agents Means are: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and aryl sulfonates and albumin hydrolysis products. Preferred examples of dispersants are lignin, sulphite waste liquors and methyl cellulose.

The active ingredient compound according to the present The invention can also be present in the formulations as a mixture with other active ingredients.

The formulations generally contain from 0.1 to 95% by weight of the active ingredient compound, preferably from 0.5 - 90 wt .-? O. The active ingredient compounds can be used as such, in the form of their formulations or in the form of preparations prepared from them, e.g. as ready-to-use solutions, Emulsions, foams, suspensions, powders, pastes, powders, soluble powders, opacifiers and granules are used will. They can be carried out in a manner known per se, e.g. by spraying, atomizing, atomizing, dusting, Scattering, gasifying, spreading with water, pickling or encrustation can be used.

The concentration of the active compound in the Ready-to-use preparations can vary within very wide limits. In general, concentrations from 0.0001 to 20 wt. #, preferably from 0.005 to 10 wt. #, used.

The active compound can also be used successfully by the ultra-low-volume (ULV) process, adopted in which it is possible to apply the formulations with 95 io content workest off compound or even the active compound alone.

If the products are applied to arable land, the amount of active ingredient is 30 g - 10 kg, in particular

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special 300 g - 6 kg, per hectare.

The present invention further relates to an insecticidal, acaricidal or nematicidal composition, velche as an active ingredient a compound according to the present invention Invention mixed with a solid or liquefied gaseous dilution and / or carrier or as a mixture with a liquid diluent and / or carrier which contains a surface-active agent, contains.

The present invention also relates to a method for controlling insects, Akari-'den and nematodes, which consists in making a connection to the insects, acarids and nematodes or to their habitat according to the present invention alone or in the form of a composition which contains the active ingredient compound according to the Invention mixed with a diluent and / or Contains carrier, applies. The present invention further relates to arable crops that counteract damage are protected by insects, acarids and nematodes by growing on arable land which immediately before and / or during the period of growth an active ingredient compound according to the present invention Invention has been applied alone or in admixture with a diluent or carrier.

It can be shown that the usual methods of protection of harvest products by the present Let invention improve significantly *

In the following formulation and bio-test examples the compounds investigated are indicated by the number of the example that indicates their preparation shows, designated.

Parts mean parts by weight.

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example (l) :

A wettable powder is prepared by pulverizing and mixing 15 parts of compound no. 6, 80 parts of a mixture (1: 5) of diatomaceous earth and kaolin and 5 parts of an emulsifier RUNNOX (product of Toho Kagaku Kogyo Kabushiki Kaisha, polyoxyethylene alkylphenyl ether). This could be diluted to a concentration of $ 0.05 by spraying with water before application.
Example (ii);

By mixing and stirring 30 parts of the

Compound No. 2, 30 parts of xylene, 30 parts of KAWAKAZOL (methylnaphthalene, product of Kawasaki Kasei Chemicals Limited) and 10 parts of SORPOL (polyoxyethylene alkylphenyl ether, product of Toho Kagaku Kogyo Kabushiki Kaisha) is an emulsifiable concentrate. This could be diluted to 0.05 ° with water before spraying on. Example (iii):

. By pulverizing and mixing 2 parts of Compound No. 8 with 98 parts of a mixture (l: 3) of talc and clay Verstäubungsmittel is prepared. This could be applied by scattering . Example (iv);

A dusting agent was prepared by pulverizing and mixing 1 part of Compound No. 3, 0.5 part of isopropyl hygrogen phosphate (PAP) and 98 parts of a 1: 3 mixture of talc and clay. Example (v):

10 parts of compound no. K, 10 parts of bentonite, 78 parts of a mixture (li3) of talc and clay and 2 parts of lignin sulfonate were mixed together. 25 parts of water were added to this. The whole was mixed thoroughly and then extruded through an extrusion granulator into granules of 20 kO mesh diameter, and these granules were dried at kO - 50 ° C.

Nit 116 -19-

7098U / 1086

Example (vi) <

In a rotary mixer, 95 parts of clay with a particle size between 0.2 and 2 mm were introduced. While rotating, the particles were sprayed with 5 parts of a solution of the compound No. 26 in an organic solvent, thus uniformly wetting the clay particles. The particles were then dried at 10 ° -50 ° C. to produce granules. Example (viih

By mixing and stirring 0.5 parts of Compound No. 18, 20 parts of VELSICOL AR-50 (high-boiling aromatic compound, product of VELSICOL CHEM.CO.) and 97.5 parts of kerosene an oily preparation was prepared *

The insecticidal, acaricidal and nematicidal effectiveness of the compounds according to the present invention is illustrated by the following Bio-Test examples.

Example A:

Test for effectiveness against larvae of Prodenia litura Fabricius.

Solvent: xylene, 3 parts by weight

Emulsifier: polyoxyethylene alkylphenyl ether, 1 part by weight

To produce a suitable preparation of the active ingredient compound, 1 part by weight of the active ingredient compound was used with the above amount of solvent containing the above amount of emulsifier, mixed and the Mixture was diluted to a desired concentration with water. In the aqueous preparation with pre-selected Active compound concentration became sweet potato leaves submerged. After air drying, the leaves were placed in a Petri dish 9 cm in diameter. Then 10 larvae of Prodenia litura Fabricius in the third larval stage were placed in the Petri dish given. The petri dish was kept at constant temperature

Nit 116 -20-

709814/1086

of 28 ° C. 2. h later the number of dead larvae was determined to calculate the degree of death. The results are summarized in Table A.

Table A.

Subscription degree (fo) for one

Concentration of the active ingredient (ppm) application no.1000 300 100

19 20 21 22 23 24 25

Nit 116 -21-

100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

709814/1086

Tabel A " 2642054 A (continued) 100 at a
Active ingredient (ppm)
100 50 Kill ^ s degree (#)
Concentration of
1000 300 100 100 Connect
application no. 100 100 100 26th 100 100 100 23 100 100 100 29 100 100 100 50 100 100 52 ICO 100 100 54 100 100 1 00 55 100 100 100 56 100 100 57 100 100 loo '■' 53 100 100 100 59 100 100 100 . ' 40 100 100 • 41 1 00 42 Comparative product:
(A) 0 Comparable product: 0
(B) Comparative product: 0
(C)

Comparative product: 30 0

Comparative product ϊ 50 0 (E)

Notation on comparative product (a):

) ₂ 0H ₃

11-C ₃ E ₇ O

i "P-KHSO-CH.

(Connection from US-PS 3,716,6oo) Nit 116 -22-

7098HM08S

Comparative product (β): CHCL

(Connection from US Pat. No. 3,716,600)

Comparative product (c):

0 CH, (C H5O) ₂ FK '''f— \

(Connection from Zh.Obshch.Khim.Vol. 36, (5) 93O) Comparative product (d):

0 CiL ₇ -IsO () ^

(Connection from GB-PS S33 863)

Comparative product (s):

0 CX

(Connection from GB-PS 833 863)

Example B; Test for effectiveness against Nephotettix

cincticeps.

Rice plants which have reached a grass height of 10 cm were planted in pots with a diameter of 12 cm each. Then an aqueous one was applied to the rice plants Preparation with the desired concentration of active ingredient compound (prepared as in Example A) in an amount of 10 ml / pot applied. After the applied preparation had dried, cages made of wire

Nit II6 -23-

709814/1088

Wickerwork of 7 cm in diameter and 1 ^ cm in height placed over the pots and exposed in them 30 female images of the Nephotettix cincticeps. The pots then vurdcn at konsifinter TempoiTitur (room temperature) fjchaltnn and 2h hours later, the number of dead insects v.urde to · calculating the degree killing determined. The results are shown in Table B.

Table B.

Concentration degree ( ^C ; O) with a concentration number of the active ingredient (ppm)

1000 100

100 • 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

7 12

14 15 17 18 19 20 21 24 30 35 36 39 AQ

Nit 116 _o,. -2k-

709814/1086

ff

Comparable products: ko O (Λ) ko O (B) 50 O (C) 100 O (D) 100 O (E)

Annotation:

The comparative compounds (a) - (e) are at the end of Tcbelle A identified.

Example G;

Test for effectiveness against calloso fracture

chinensis.

The bottom of a Petri dish with a diameter of 9 cm was covered with filter paper, whereupon 1 ml of an aqueous preparation with the desired concentration of active compound (prepared as in Example A) was applied. Then 20 Callosobruchus chinensis beetles were placed in the Petri dish and this was left to stand at constant room temperature at 28 ° C. for 2k hours. After 2k h, the number of dead beetles was determined in order to calculate the degree of death. The results are shown in Table C.

Kit 116 -25-

709814/1088

Table C.

Connection kill rate (° / c) at a concentration no. Of the active ingredient (ppm)

1000 100

2 100 100

4 100 100

8 100 100

13 100 100

17 100 100

18 100 100

19-100 100

20 100 100

21 100 100

25 100 100

26 100 100

27 100 100

28 100 100

29 100 100

30 100 100

31 100 100

32 100 100

33 100 100

34 100 100

35 x 100 100

36 100 100

40 100 100

41 100 100

Comparison products

(A) Nit 116 O 0 -26- (B) O 0 (C) O (d) 100 (E) 100

709U4 / 1088

Note : The composition of the comparison compounds (a) - (ε) is given at the bottom of Table A.

Example D;

Test for effectiveness against larvae of Culex pipiens pallens Coquillett.

100 ml of an aqueous preparation with a preselected concentration of active ingredient / compound was placed in high-λ.-area Petri dishes 9 cm in diameter. In these bowls 25, each in the k. Larvae of Culex pipiens pallens Coquillett at the larval stage were introduced, and then the dish was placed in a constant temperature room of 28 ° C. 2k h later, the number of dead larvae was determined to calculate the degree of destruction. The results are shown in Table D.

Table D:

Connect No. manure 1 3 4th 5 8th 9 0 Λ 1 1 2 1 3 1 5 1

Degree of destruction ( ^c / i) at a concentration of the active ingredient (ppm)

1 O ₄ y. 0.01

100

100

100

100

100

100

100

100 100

100 100

100

100

Nit 116 -27-

7098U / 1086

Table D (continued)

Verbin- degree of destruction ( ^c / o) at a concentration dung No. of the active ingredient (ppm)

1 0.1 0.01

Ib 100 0 19th 100 0 20th 100 0 21 100 0 22nd 100 23 100 24 100 25th 100 26th 100 27 100 28 100 29 100 30th 100 31 ■ 100 32 100 33 1G0 34 ^: 100 36 100 39 100 4o 100 4i ■ ioö 42 .100 Comparable products: (A) (B) (C) (D)

100 100 100 1 00

100

100 100

Anme rk ■ "- clothes:

The comparative compounds (a) - (e) are described at the bottom of Table A.

Nit 116 -28-

7098U / 1086

3t

Boispiol E.

Tost regarding the effectiveness against Plattella {jerraanica.

The bottom of a Petri dish 3 cm in diameter was covered with filter paper and 1 ml of an aqueous preparation with a preselected concentration of active ingredient compound (prepared as in Example A) was added to this filter paper. Then the Petri dish 10 Iraagos of Blattella germanica was introduced and the Petri dish was left to stand in a room with a constant temperature of 28 ° C. for 2 hours. After 2k h, the number of dead imagos was determined in order to calculate the degree of destruction. The results are shown in Table E.

Table E.

Connection degree of destruction (fo) at a concentration dung No. of the active ingredient (ppm) 1000 100

1 100

2 100

5 100

4 100

5 100

6 100 8 100

15 100

100 100 100 100

-29-

7098H / 1086

1 5 Nit 116 1 7th 1 3 20th

Table E (continued)

Connection kill degree {° / o) at one concentration

dxing no. of the active ingredient (ppm)

100 100

25 100

25 100

26 100

27 100

28 100

30 100

31 100

32 100

33 100

34 100

35 100

36 100

37 100 58 100

39 100

40 100

41 100

Comparison products

(A) 0

(B) 0

(C) 0
(D) '0
(E) 0

Nit 116 -30-

709814/1086

Annotation:

The comparative compounds (a) - (e) are at the foot of the Table A described

Example F

Test regarding 1 i of the effectiveness against Musca domestica

vioina.

A filter paper was placed on the bottom of a Petri dish 9 cm in diameter, and then 1 ml of an aqueous preparation of the desired concentration was applied
Active ingredient compound (prepared as in example Λ) added to the bowl. Ten female imagos from Musca
domestica vicina were placed in the petri dish. The Petri dish was then left to stand in a room at a constant temperature of 28 C for 2k h and the number of Imagos killed was then determined in order to calculate the degree of destruction. The results are shown in Table F.

Table F.

Connection degree (° / o) at a concentration

Application No. of the active ingredient (ppm)

1000 10C)

1 100

2 100 100

3 100 100

h 100

5 100 100

6 100

7 100

8 100 100 10 100

12 100

13 100 100

lh loo

Nit 116 -31-

7098U / 1086

T.-bolie F (continuation length)

Verb in degree of destruction (/ ό) at a concentration

Application No. of the active ingredient (ppm)

IQOO 100

15 100

16 100

17 100

18 ■ 100 '100

19 100

20 100

21 100

22 100

23 100

24 100

25 100

26 100

27 100

23 100

29 100

30 100

31 100

32 100 35 100 .100

34 100

35 100

36 100 ^ O 100 hl 100

JNTit 116 -32-

709 8 U / 10

Comparison products

(A) O

(B) O

(C) O

Note: The comparative compounds (a) - (c) are on At the bottom of Table A.

Example G

Test for effectiveness against the two-point spider mite, (bean mite) Tetranychus telarius (spray test).

The leaves of kidney beans at the two-leaf stage i were infected with % O - 100 Imagos of Tetranychus telarius (a strain resistant to organophosphorus compounds). The bean plants were then cultivated in pots each 9 cm in diameter. 2 days after infection, an aqueous preparation with a preselected concentration of active ingredient compound (formulated ivie in Example A) was sprayed over the leaves in an amount of 20 ml per pot. The pots were then placed in a greenhouse, and 10 days later the acaricidal effect was evaluated, including according to the following scale.

3-0 "/ ο survivors

2: not more than 5 ^c / ° survivors based on untreated control plants

1: 6 - 50 % survivors, also based on untreated control plants

0: more than 51 ° / ° survivors, based on untreated control plants

The results are shown in Table G.

Nit 116 -33-

709814/1086

Table G.

Combination control action in the event of an active ingredient

cking no. centering of (ppm)

1000 300 100 50 10

1 '2

10 11 12 13 ■

15th 16 17th 18th 19 ·· 20th 21 22nd 23 24 25th 26th 27 23 29 30th 31 32 33

Ni t. 116 _ ₃ z, ._

709814/1086

3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 2 3 3 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 2 3 3 3 3 3 3 3 3 3 3 3 3 2 3 3 3 3 3 3 3 2 3 3 3 3 3 2 3 3

Table G (continued)

Combination control effect in the case of an active ingredient concentration No. tration of (ppm)

1000 300 100 ^ O 10

3 3 3 3 3 3 3 3 3

3 3 3 3 3 3 3 3 3

3 3 3 3 3 3 3 3

Comparable products:

(A) 0

(B) 0

(C) 0

(D) 0

(E) 0

Note: The comparative compounds (a) - (e) are described at the bottom of Table A.

Example H

Test for effectiveness against the two-point spider mite, (bean mite) Tetranychus telarius (immersion test)

The leaves of kidney bean plants at the two-leaf stage were infected with 50-100 imagos of Tetranychus telarius (strain resistant to Organopho spho rve rbindungen), 2 days later, an aqueous preparation with a preselected concentration of active ingredient compound (formulated as in Example A) by watering the roots of the bean plants, each supplied in an amount of 20 ml / pot. Then were placed the pots in a greenhouse and 10 days later

Nit 116 -35-

7098H / 1086

the acaricidal effect was determined according to the following scale:

3: O fo survivors

2: not more than 5 ^r / o survivors, based on unrelated

handelfce confectionery plants
1: 6-50 ^c / o survivors, based on untreated

Confectionery plants
0: flour 'as 5I ° / ° survivors, based on untreated

Control plants

Table H shows the results

Table H.

Combination control effect with an active ingredient concentration

tion no. tration of (ppm)

1000 300 100 50 10

1 3 3 3 2 3 3 3 3 3 3 3 4th 3 3 5 3 2 D. 3 7 ■ 3 8th 3 3 3 13th 3 3 3 H 3 3 2 15th 3 3 3 17th 3 5 3 18th 3 3 21 3 3 22nd 3 3 23 3 2 24 3 3 3 25th 3

Nit 116 -36-

7098U / 1086

Tabel !! (Continuation)

Combination effect with an active ingredient conduit No. Concentration from (ppm)

1000 300 100 -> 0 10

3 3 3 3 3 3 3

3 3

26th 30th 31 52 35 36 . 40

Comparable products:

(A) 0

0 0 0 0

Note: The comparative compounds (a) - (e) are on Described at the end of table Λ.

Belsoiol I

Test for effectiveness against Meloidogyne incognita acrita.

A preparation of the active ingredient was produced by pulverizing and mixing 2 parts by weight of active ingredient compound with 98 parts by weight of talc. The active ingredient compound prepared in this way was added to soil infused with Meloidogyne incognita acrita in such amounts that in each case concentrations of 50, 25 _} 10 and 5 ppn * were obtained. The mixture was stirred and mixed well and then placed in pots, each with an area of 0.0002 a. 20 seeds of tomatoes (variety: KURIHARA) per pot were sown into the soil pretreated in this way. The tomatoes-

Nitllö

-37-

709SU / 1086

seeds Λν were grown to plants in the greenhouse, k weeks later the roots - without damaging them - were pulled out of the earth and the damage to 10 roots was determined on the basis of the following scale to determine the root knot index.

Degree of damage:
0: no root knot formation - perfect control

f ungs effect

1: slight root knot formation 2: strong root knot formation
4: largest root knot formation - corresponds to one

Non-treatment

τ, -, - iu j (degree of damage χ number of roots) _ root node xndex = / A, '\,,, .- ^ j. _ir ι \ ι.

(Total number of roots tested) 4

From this formula the control effect was obtained:

r.irootnodeindex \ _ / rootnodeindesx! , of unbeh. SurfacesT Ivon beh. Surfaces ; Control _{effect = ¥ urzellcno fcenindex of} ^ nth area

The 100 % control effect means perfect control.

The results are summarized in Table I.

Table I.

Combination control effect in the case of an active ingredient condensation No. Concentration from (ppm)

'^ 2 50 10 5

Nit 116 -38-

7098U / 1086

100 100 100- 100 100 100 100 100 100 1C0 100 100 100 100 100 100 100 100 100 88.0 100 100 100 100 100 100

Table I (continued)

Connect
application no. Control effect
concentration of (ppm)
50 2 ~) ~ 100 one
10 I / irks open
's 9 100 100 10 100 100 11 100 100 12th 100 100 '13 100 100 100 14th 100 100 15th 100 100 95.2 16 100 95.0 17th 100 100 100 18th 100 100 100 100 19th 100 100 20th 100 100 100 82.5 21 100 100 100 88.3 22nd 100 100 23 100 100 100 83.6 24 100 100 25th 100 92.9 26th 100 27 100 100 2S 100 100 29 100 89.1 30th 100 95.0 31 100 97.5 32 100 100 33 100 100 54 ' 100 74.7 35 100 100 100 36 100 100 " 100 . 37 100

Nit 116 -39-

7098U / 1086

Table I (continued)

Vc rblndnnj 38 Control effect 25th ; in the case of an active ingredient 10 5 No. 59 concentration of 70.7 (ppm) 40 50 100 70.0 41 100 100 100 100 42 100 100 64.3 Comparisons 100 100 74.0 Products : 100 (A) 100 (B) (C) (D) 0 0 0 22.3

Note: The comparative compounds (a) - (e) are described at the bottom of Table A.

The following Herste.llungsbeispiele illustrate the process for the preparation of the compounds according to FIG present invention.

Example 1 ;

ο 9h

Oo - (' ^X V ei

^S "2 -S ^ J-

37 g of potassium O-ethyl-N-methyl-N-4-chlorobenzenesulfonyiphosphoramidothioate were dissolved in 150 ml of methyl ethyl ketone and lk g of n-propyl bromide were added. The mixture was heated to 60-70 ° C. for 3 hours and the reaction was brought to an end. After the methyl ethyl ketone had been distilled off, toruene was added to the residue and the mixture was mixed with water and 1 % g of aqueous

Nit II6 -h0-

7098U / 1086-

Sodium hydroxide and washed again with water. After distilling off the toluene under reduced pressure 31 g of O-ethyl-S-n-propyl-N-methyl-N-4-chlorobenzene. ^ sulfonyl phosphoramidothiolate in the form of a colorless oil

20th
η _ = 1.5335 obtained.

Example 2:

P-N (2)

5.6 g of potassium hydroxide was dissolved in 100 ml of ethanol, and the solution was saturated with gaseous hydrogen sulfide at room temperature to obtain an ethanolic solution of potassium hydrosulfide. 26 g of 0, O-diethyl-N-methyl-N-methanesulfonylphosphoramidothioate were added to this solution and the mixture was stirred at 75-80 ° C. for h. The internal temperature was reduced to about 40 ° C. by cooling, then 14 g of n-propyl bromide were added, followed by stirring at 65 ° C. for 3 hours in order to complete the reaction.

The volatile components were removed from the reaction mixture under reduced pressure, then toluene became added to the residue and the mixture was washed with water, 1 / £ aqueous sodium hydroxide solution and again with water washed. After drying the mixture over anhydrous sodium sulfate, the toluene was removed and it - ■ urden 22 g of O-ethyl-S-n-propyl-N-methyl-N-methanesulfonyl-

phosphoramidothidate in the form of a colorless oil

= 1.5020 obtained.

Example 3: ° 2 ^Η 5 ° \ 0

(3)

CH ₂ CH ₂ Nit 116 -41-

7098 14/1086

CH ₅ CH ₂ CH ₂ S

21 g of sodium methanesulfonanilide were in 150 ml Suspended toluene and there were 10 g of O-ethyl-S-n-propylthiophosphoryl chloride admitted. The mixture was then heated to 80-90 ° C. for 3-4 hours to complete the reaction to lead. After the completion of the reaction, the mixture was cooled down to room temperature and washed with water, thereafter with 1 $ sodium hydroxide solution and again with water. The mixture was dried over anhydrous sodium sulfate. Then the dried reaction mixture became under reduced pressure the toluene, distilled off and it 25 g of O-ethyl-S-n-propyl-N-phenyl-N-methanesulfonylphosphoramidothioTat obtained in the form of a colorless oil nj = 1.5 ^ 00.

The following compounds were prepared by Method u
obtain.

analogous to those described in the previous examples

Nit II6 -42-

709814/1086

H· et

H H

Table 1

O CD CD

O CD CD

'Connection No.

4 5 6

10

11

R ¹

c:

C _n H,

• 5

C ₂ H ₅

C ₂ H ₅

H ¹ O. S

(D

CH ₃ OH ₂ CH ₂ S '

CH, CH,

R-

/ Λ

1st floor

OCE

Phys ikalis ohe Characteristics

Cl.

1.4985 1.4952 1.5245

Ί; 519Ο

, 1.5294

1.5350

1.5456

n | ° 1.5572

Table '1 (continued)

H-d-

H H

O OO CO

Connection: No.

R-

12th

13 H 15

16

17 18

19 20

21 22

C ₂ H ₅

C _f

O ₂ H ₅

ca,

CH ₂ CH = CH ₂
CH ₂ CH = CH ₂

² J /

CH,

CH ₂ C ₁ I.

CH ₃

Physical
Characteristics

1.5420

1.4972 1.5010 1.5009

1.5337

1.4898 1.5038

1.5404 1.5550

1.5371 1.5367

H-c +

Table 1 (Fortsot '/ unff)

-J O CO

Connection no ..

24

CiH-,

Y / V

Cl

CH.

CH.

Phy 3 ikalis ehe 'characteristics

. 1.5380

1.5444

CH,

CH

■ A

CH

■ 7t.

rl

H H

σ »

32

Tabnllo 1 (Fort sot

Connection R

'No.

36 C ₂ H ₅ 27 ^C 2 ^H 5 28 C ₂ H ₅ 2'9 \ C ₂ H ₅ 30th C ₂ H ₅ 31 C ₂ H ₅

CH

.C

-O

CH.

σι

CH

CH.

CI

H ₅

^CH

CH ₂ Cl

Cl

Pliy s ical is before characteristics

1.5359 1.5300

1.5390 1.5429

Ι.5Ο75 1.5532

XJ

m.p. 99 -

example

s - tr (25)

CH-CH ₀ CH ₀ S SO ₀ CH- i;> 2 2. 2 3;

13 »1 g of sodium N-'Methylmethanesulfonainid imrden suspended in 100 ml of acetonitrile. Then 21.9 g of O-ethyl-Sn-propyldithiophosphoryl chloride were added at room temperature and, after slow heating, the mixture was stirred at hO-50 ° C. for 4 hours. After the completion of the reaction, acetonitrile was evaporated and toluene was added to the residue. The mixture was then washed with water, with 1 / o aqueous NaOH solution and again with water. After drying the toluene layer over anhydrous sodium sulfate, the toluene was removed under reduced pressure and then at 70 ° C. for a further hour / i mm Hg dried and there were 22 g of O-ethyl-S-npropyl-N-methyl-N-methanesuironylphosphoramidodithio ^ at

20 in the form of a colorless oil n ^. = 1.52-95 obtained.

The following compounds were obtained in an ancestral manner similar to this example.

Nit 116 -47-

709814/1086

Doorbell 2

σ
oo
co

c +

H
H

Link; No.

34 35

Sl

"3" 8 39

40 41 42

C ₂ H ₅

R ¹ 0 SR ²

\ it /

■ P - N.

(D

^S0 2 ^R

CH

CH,

CH,

1-O ₃ H ₇ . , -CH ₂ CH = CH

■ o

Physical Skills.

n ²⁰ 1.5214 n ²⁰ 1.5440

ng ^u 1.5535

1.5735

η ²⁰ 1.5220 η ²⁰ 1.5060 η ²⁰ 1.5245 η ²⁰ 1.5410 "20th
»Ι) 1.5530

Claims (1)

Claims represents wherein A C - C ^ alkyl or halogen, m 0,1,2 or 3 and R Cj-Cg alkyl, which is optionally substituted by halogen or by a group of the general formula is substituted, wherein B is halogen, C -Cg-alkyl, nitro or C -Cg -alkoxy, k 0, 1, 2 or 3 and X oxygen or Mean sulfur. 2. Process for the preparation of the phosphoric acid amide esters of the general formula I, characterized by that a) a phosphoramidothioate salt of the general formula I _1/1 \ ■ R ¹ O * -s .1-1 .1 -49- 7 0 9 8 U / 1 0 8 B. 12 3
above R, R and R are as defined in claim 1 and M is an alkali metal atom or ammonium, with an alkylating agent of the general formula CH ₃ CH ₂ CH ₂ .Y (III), wherein Y is halogen or the sulfonic acid group, is reacted, or that b) a thio (or dithio) phosphoryl halide compound of the general formula R ¹ 0 _χ Χ P-HaI (IV), CH ₅ CH ₂ CH ₂ S wherein R and X are as defined in claim 1 and Hal is halogen, with a sulfonyl amide salt of the general formula R ²
M ² -N ^ (V), 2 3 wherein R and R have the meaning given in claim 1 and M represents an alkali metal atom. 3. Insecticidal, acaricidal or nematicidal agent, characterized by a content of at least one phosphoric acid amide ester according to claim 1. k. Process for combating insects, mites or nematodes, characterized in that phosphoric acid amide esters according to Claim 1 are allowed to act on the insects, mites or nematodes or their habitat. -50- 709814/1088 5. Use of phosphoric acid amide esters according to Claim 1 for combating insects, mites or nematodes, 6. Process for the production of insecticidal, acaricidal or nematicidal agents, characterized in that that phosphoric acid amide ester according to claim 1 is mixed with extenders and / or surface-active agents. -51- 7 0 9 8 1 /./ 1 0 8 8